Hydrogenation process



R. J. BYRKIT, ,IR l 2,174,651

HYDROGENATION PROCESS Oct'. 3, 1939.

Filed May 17, 1957 3 Sheets-Sheet 2 K//H//M 6 2 ROLLIN J. BYRK|T,JR.

ATTORNEY Patented ct. 3,1939

PATENTn oFFlCE HYDROGENATIONv PROCESS Rollin, J. Byrkit, Jr., Marshallton, Del., assignor to Hercules Powder- Company,

D`el., a corporation of Delaware pplication May 17, 1937, Serial No. 143,193

Wilmington,

REISSUED 15 claims.y (o1. 26o-100) S This invention relates to a process andV apparatus forthe continuous hydrogenation of un-l saturated organic compounds and more particularly to a process and apparatus for the continu- 5 ous hydrogenation of resins and other compounds which are difficult to hydrogenate. l

Heretofore the hydrogenation of rosin has not been successfully accomplished from a practical standpoint, although they desirability" of hydrogenatedrosin has long been known, as shown by United States Patent 1,249,050 lto Ellis and United States Patent 1,167,264', to Brooks. 'I'his has been due to the great difficulties involved and to limitations imposed` by the development of the art of hydrogenation.

The hydrogenation of rosin in a batch or noncontinuous process has been suggested heretofore,

but has no-t met withA commercialsuccess. In such-a process the rosin is placed in a closed vessel, as, for example',v an autoclave, together with the catalyst in the form of ainely divided powder and hydrogenadmitted underl pressure.

The conditions of temperature and hydrogen v pressure are'adjusted to meet the requirements of 25. the 'hydrogenation process, and after a lapse of sufficient time the hydrogenation is more or less complete. y

Fromv the commercial or economic standpoint,

,l and even from a technical standpoint, such nonv continuous hydrogenation procedureis subject rto many disadvantages, certain of which are due to the :ion-continuous nature of the process and others of which are due to the type of catalyst.`

necessarily employed. Still other [disadvantages 35. are due to the characteristics of-rosin, such as' Among 'its physical state and active acidity.

these disadvantages of processes for the hydrogenation of rosinheretofore. practicedthe folthe" time required for a complete cycle of operations, since during the charging of the hydrogenation vessel, filtration and recovery of the filtered catalyst, the catalyst performs no useful The catalyst is in service for only a portion of function. In fact, the catalyst is often harmed .by the exposure and necessary handling.

Because of this necessary handling and exposure the useful life of the hydrogenation catalyst is greatly shortened and its activity declines` morezrapidly than wouldbe the case if it were subjected only to the use incident to hydrogenavtion. The diminution in activity of the catalyst is, in fact', due largely to the discontinuity of the hydrogenation and they active acid nature of the rosin. Furthermore, when'the useful life of the catalyst is at an end .it must be discarded; since the requisite reworking necessary to t it for further use constitutes a greater expense than the procurement of new catalysts.

-When a hydrogenation catalyst is used in a non-continuous hydrogenation process it is found that, unless it be a noble metal catalyst, the hydrogenated rosin produced` is contaminated to an appreciable extent by the catalyst, and. so farV hydrogenation lwith noble4 metal catalysts has been used only as an instrument of laboratory technique due to its high cost. VThis contamination occurs each time theA catalyst is used in the process with a corresponding lossof catalyst. Accordingly'the hydrogenated rosin produced is contaminated in this manner, and the catalyst lost.

Because ofthe difficulties occasioned by the separation of catalyst from `the hydrogenated rosin it is practically essential to maintain the ratio of catalyst to the rosin to be hydrogenated as low as possible. However, it is known that the rate of hydrogenation is usually in this, type of r hydrogenation proportional tothe amount of catalyst present. Accordingly, maintaining a low catalyst ratio, While economically and practically necessary in non-continuous procedure, is ex It is Iimpossible to maintain the activity of the amount of catalyst which can be filtered and handled in the process.

" The successful, commercial hydrogenation j.of rosin involves thehandling of large volumesof material. Since such hydrogenation requires the use of high hydrogenation pressures, the size of the autoclaves required for commercial operation though continuous hydrogenation in the liquid phase has heretofore been carried out, the application has been limited to compounds which readily combine with hydrogen, and do not have a markedly unfavorable action upon the catalyst or where very high temperatures are used in connection with rugged, `but relatively inactive, catalysts as in hydrogenation of petroleum. Such procedure has not been successful when applied to rosin. This is due in part to the extreme diflculty of hydrogenating the second double bond in the hydrocarbon nucleus of rosin acid which makes the hydrogenation of rosin and compounds containing a rosin` acid nucleus to highly saturated materials extremely' diicult, and in part to the very markedvaction of rosin and other chemically active compounds containing a rosin acid nucleus upon the types of catalysts hereto- 'fore used in vcontinuous liquid phase hydrogenatin. Y It is the object of this invention to avoid these difficulties and to provide an eflicient and economical process adapted for commercial operation by which unsaturated organic compounds, normally dicult to hydrogenate, may be vcorrtinuously hydrogenated to a relatively high and uniform degree of saturation. Itis; a further object of this invention to provide an apparatus in which this method may be conveniently and eciently carried` out. f Y t In accordance with the process of this invention, an unsaturated organiccompound or other l organic compound capable of hydrogenation'in the liquid state is passed continuously through a."

plurality of reaction vessels or reactors packed with a stationary hydrogenation catalyst such as, Afor example, pellets of an activated nicklealuminum alloy catalyst, in each of which the unsaturated compound iscontacted with hydrogen at suitable pressure and temperature. In carry.

ing out this process I pass the unsaturated compoundthrough the plurality of reactors at a rate which may be varied directly with the activity of the catalyst until the activity of the catalyst becomes so low that the rate of ow is too slow to be practical, and then replacethe spent catalyst in the-flrst reactor with fresh catalyst and rearrange the order of the reactors so that this first reactor becomes the last or iinal reactor and the reactor which was second no w becomes the The process is then continued until the rate again becomes slow and again-the 'catalyst in the reactor which is-now rst(ori1gnall`y lsecv ond) is'replaced, the reactor placed at the end in the presence of the least ac tive catalyst/land' of the process, 'and the second-reactor (originally third) made -the first/This is then repeated periodically as long as the process is continued, andA after each recharging the rate of flow may be stepped upto approximately its original value. Y

In this way, I obtain a cyclic process in which the untreated compoundl is first hydrogenated thensuccessively treated nftlre presencaof ylgts of catalysts of greate. and \\greater activity.

Furthermore, Iv'obtain a' proc in wh/ihany are, present in the 4material being hydrogenated .are trapped by the catalyst which is most nearly spent and, hence, least valuable.

Thus, I obtain a maximum eiiiciency ofhydrogenation for thex'amount of catalyst used and produce uniformly hydrogenated products over long periods of time. 1

'I'he hydrogen may, if desired, be admixed with the material being hydrogenated as it enters the first reactor and flow concurrently with the material through the entire series of reactors. This is the most convenient method of operation and I prefer to use it. Alternately, the hydrogen may be introduced into each of the'reactors separately and oW either concurrentlyY or counter-currently to 'the direction of flow of the material being hydrogenated. Again the hydrogen Ymay be introduced into the final reactor and flow countercurrently throughout the series of reactors.

The process in accordance with this invention is suitable for the hydrogenation of an unsaturated organic material which is a liquid at the temperatures and pressures required for hydrogenation, or which may bey put into solution in a suitable solvent, and is particularly adapted tor the hydrogenation of 'a rosin such as, for

example,v wood rosin, American gum rosin,

lFrench gumgrqsin, etc., and for the hydrogenation of compounds which contain the hydrocarbon nucleus of a rosin acid, such as, for example, esters of a rosin acid witha monohydric or polyhydric alcohol, as, methyl abietate, ethyl abietate,

glycerol abietate, etc., the alcohols produced by action upon catalysts available,y and nature of the end product or products. desired. For example, in the continuous hydrogenation of rosin and other abietyl compounds in accordance with this invention, the atalystqmay be produced byA alloying together nickel and aluminum, comm'inuting,the resultant alloy into. particles or fragments of the desired side and then treating the. alloy with hydrogen or with an alkaline solution, such as sodium carbonate or sodium hydroxide solution to activate the surface of the alloy. The production of this catalyst is described more fully'in United States Letters Pat-A ent No. 1,628,190, dated May Y 10, 1927, and 1,915,473, dated June,- 27, 1933, issued to Murray Raney.

In forming the nickel-aluminum alloy which the catalyst is made itis often desirable to include in thealloy a relatively small amount of other metal as; for example, copper, zirconium, cerium, cobalt," etc., which acts as a'promoter and increases the activity of the resultant catalyst for certain hyldroge'nations. The activity of from the catalyst may also be enhanced by heat-treating the alloy, asY by annealing, quenching, etc.

i For the hydrogenation of unsaturated organic compounds inv accordance with this invention,

the nickel-aluminum alloy which may contain` other rne'tals'as promoters, or which may have been subjected toA heat treatment or both, is used in the fo'rm of particles or fragments graded .to

catalyst poisons which may and frequently f a size which will pass through holes in a perfo-w tained on a perforated plate having holes 1%" in diameter, and preferably of' a size that will passY through holes in a perforated plate having a diameter of 1A and be retained on a perforated' plate having holes 1%2" in diameter.

'I'he most desirable size of the particles of the alloy is controlled by two opposing'sets of factors. High yield of catalyst,. low loss in activation and the tendency of the stream of the material being treated to pick up small particles of the alloy, suggest the use of large particles. On the other hand, high efliciency of hydrogenation, bothl as to degree' of saturation and as to'rate of production, suggest the use of fine particles. I 'have found in my process that the range of sizes passed by a plate perforated with 1A" holes, but retained by a plate perforated with im holes gives the maximum efficiency inA actual operation.

The catalyst alloy may be obtained in particles or fragments of the desired size by a "shotting operation from `the moltencondition, or by 'casting the alloy in' masses of a larger size and then crushing, as,for example, by rvmeans of a jaw crusher. After the grading operation, the particles which are too large may be further reduced in size or remelted, and the particles which otherwise as described in the Rainey patents and charged Vvinto the hydrogenation equipment@ Since the catalyst after activation is intensely active and indeed pyrophoric in nat-ure, it must be transferred to the hydrogenation equipment covered withfa lm ofl water or other protective coating. Alternatively, the unactivated alloy may be charged into the hydrogenation equipment and be activated therein, as, for example,` by treatment with an alkali solution. i If an alkali i solution is used, the activated catalyst in place in the hydrogenation equipment will be washed free of alkali andother'for'eign substances'with water and then dried by being heated in a ciment of an inert gas, vas, for example, a current" of hydrogen, super-heated steam, "etc., or by displacement bysuitable solvents as alcohol, acetone, etc.

Having now indicatedin a general way the nature and purpose of my invention, I will proceed to a more detailed description' thereof, by reference to the accompanying drawings, vin

which: Y

Figure 1 is a diagrammatic view of the preferred'embodiment of the apparatus in accordance with my invention, which I shall term the concurrent, lip-flow apparatus,`

Figure 2 is a vertical sectional view of one form of a reaction vessel or reactor in which hydrogenation is carried ou't in my process and' which is used in the apparatus shown in Figure 1,

Figure 3 is a schematic view of an alternative arrangement of the apparatus in accordance with rent down-flow apparatus, and

Figure 4 is a schematic Jviewof a second alter- A n native arrangement of the apparatus in accordance with this inventionpwhich I shall term ,the counter-current down-now apparatus.

The preferred form of my apparatus, shown diagrammatically in Figure 1, consists of a reservoir I'for the unsaturated material'tobe hydrogenated, which when used with an unsaturated material which is solid at room temperature, such Irated plate having a diameter of y2", and be reas rosin, will be lprovided with a heating means,

for example, an electrical heating coil, to maintain its contents at a suitable elevated temperature. The reservoir I is connected by a conduit 2 to a variable-feed pump 3. vThe pump 3 is connected on the outlet side to 'a conduit 4, which is capable of withstanding vhigh pressure, and which is in turn joined at 5 by a hydrogen inlet .line 6 which is provided with a valve 1. The line 4 is provided with an pressure gauge 8, and is connected with the lower end of each of a plurality of reaction vessels 9, I0, I I, I2 and I3,

through the valves I4, I5, I6, I1 and I3.

The reaction vessels or reactors are packedl with a stationary hydrogenation catalyst, as for example, particles of nickel-aluminum alloy which have been treated to render them catalytically active as described hereinbefore. The

reactor may be of any suitable design, such as,-

nickel steel or it may befconstructed of another metal, for example, ordinary steel, and lined with chrome-nickel steel. 5

The reactor shown in Figure 2 consists of an elongated tube I9 provided at each end .with

iianges 20, to which are removably attached a top-plate 2| and bottom-plate 22, each of -which is provided with a sealing gasket 23, 23 which may, for example, be made of annealed copper or other suitable material. Both the bottom-plate 22 and the top-plate 2I are provided with openings 24, 24 for attaching conduits for the incoming and outgoing materiall being Fhydrogenated.' The 'bottom-plate 22 is provided with a well 25'adapted to contain a thermocouple or other temperaturemeasuring device. l `The reactor will be provided with some means of .-heating, as, for example, an electrical resistance unit wound around the outside with suitable inprovided with apressu're gauge 3 I- and with the- .valves- 32, 33,' 34, 35 and 3,5, respectively, and connected to the conduit 31 which is in turn connected to a high-pressure type gas-liquid separator 38. The liquid outlet of the separator 3 8 is connected through'a conduit 39, provided with a valve 40, to a low-pressure' type gas-liquid separator 4I provided with a liquid outlet 42. T he gas outlet ofseparator 38 is connected to a vconduit 43 provided with a pressure reducing valve 44. The gas outlet of :separator 4I is connected to a conduit 45, provided with a valve 46 and in turn connected to the conduit 43. The conduit 43 is provided on .the outlet side of its junction with conduit -45 with a valve 41 con^ tinue'd to a fis-compressor and storage tanks.,

The inlet conduits of each of the reactors 9, III, II,v I2 and I3, respectively, are connected 4by conduits' 43, 49, 50, 5I and 52, respectively, through the valves 53, 5 4, 55, 56 and 5T, respectively, to the outlet conduits 3 0, 26,v 21, 28 and 29, respectively, of the 'reactors I3, 9, I0, II and I`2, respectively.

Each of .the reactors is vsurrounded with an electrical heating coil orotherwise heated, as for In startingthis apparatus into operation for A the hydrogenation of an unsaturated material, such as, for example, rosin, each of the reactorsA 9, I0, Il, I2 and I3 is charged with a stationary hydrogenation catalyst, such as, for example,

activated nickel-aluminum catalyst to ll the yreactor to a point near the top, the catalyst .being at all timesV kept out of contact with air by keeping it hooded with an inertvolatile liquid, such as,for example, water. After the charging operation the reactors are sealed into place L and the inert liquid blown out of the catalyst valves, Vpassed up through one of the reactors, for example,'reactor 9 in which themixture of rosin l after passing throughdshe rst reactor, the mix- 1 by a stream of ,inert gas. When Athe catalyst is dry, rosin in the molten condition is forced by the pump 3 through 4the conduit I and is joined' by astream of hydrogen at 5. This admixture. is then by the proper adjustment ofthe various and hydrogen flows up through the catalyst and the rosin partially reacted with the hydrogen,

ture of hydrogen and partiallyv hydrogenated rosin is passed to the bottom of another reactor.

Thus, fromreactor 9, the mixture could be4 passed through conduit I9 and then up through reactor l0, by closing valve ,32- and opening valve 54, The mixture is then passed in turn through each of the reactors in this way and finally flows; throughconduit I1 to the vseparator 38 in which` the gas phase' (hydrogen) -is separated from the liquid phase (hydrogenated rosin containing ,dissolved hydrogen). The hydrogen` passes out through conduit I3.` The4 liquid phase passes through-conduit 39 tothe separator 4I in which the dissolved hydrogen comes out of solution due to the lower pressure and is separated from the hydrogenated rosin. This hydrogen passes out through conduits 45, and A43 in whichit is joined by the hydrogen from separator 38, and then passes to a compressor and then tanks, invvhich'v it is stored for .further use. Alternately, the ex` cess hydrogen may be circulated around the system bylmeans of a suitable pump, rather vthan expanded, and 4 then recompressed 'for further use. The hydrogenated rosin passes out through conduit 42 to containers for shipment or storage tanks as maybe desired. Y

The sequence' in whichthe mixture of rosin and hydrogen llows through the'reactors will def pend upon'the positions of various valves in the various conduits. In Table I, I have tabulated the positions of various valves which control the direction of flpwnece'ssary to secure the. various Y sequences of reactors which may be followed'in the course of along continued operation.

During the use of anygiven series of reactors the ,extent of hydrogenation of the'unsaturated by decreasing the rate or ow of the mixture of the unsaturated material and hydrogen through the reactors. When this rate ofv flow becomes too slow to be economical, or ifa higher degree of saturation is desired; the first reactor of the sequence is charged withfresh catalyst and the voperation continued using a sequence in which the freshly charged reactor is thenal reactor.-

Thus, referring to Table I, if reactor sequence A material may be maintained at :1 -uniform level.

was inuse and then interrupted, for example,

because the rate had become slow, the reactor 9 would be charged with' fresh catalyst, and opration resumed using the reactor sequence B. It is not; as will be appreciated, necessary to'discontinue operations While one or more reactors which are diilicult to hydrogenate it is essential to proceed within rather denite ranges of conditions toobtain-a suflicietly high degree of saturation to be of "value Rosin is an example of a compound which is diilicultl to hydrogenatav while acetone is an 'example of one which is easily hydrogenated. l Thus, for example, under a tions, .while `the first double bond in rosin and other rosinyl compounds can be hydrogenated at temperatures of vabout C. and hydrogen pressures of about 100 lbs. or less per square inch,

satisfactory hydrogenation of-the second double etc., temperatures as low as '10P C. and hydrogen pressures as low as 100 lbs. per square inch may be used with satisfactory results.

given set of condi- For the hydrogenation of. rosin-in the molten condition, I 'have found that it is desirable to use a temperature within the range of about'v C. to about 300 C and a hydrogen' pres-- sure in excess of 1-000 lbs. per squareV inch, and

preferablya temperature within the range of Table of saturation secured, but ordinarily theadvan- Valvenumberi Reactorseqnenee-.- l Y 14 15 11s-11` 1s 32 sa a4 as as 53 54 55 se. 57

A n-1o-11"12'-1a)1 o o c c c c c c c o c o o o vo B io-n-iz-ia-o-- c o c o c o o o c o o o. o o o g o c -o c cV o o c o c o o o .o o o c c o` o c c o c o -o o o o o c o c uc o c c o o c o o o o c.

oiudimdtmvnlvebecmed.

0 indicated the valve be open.

about 180 C. to 220 C. and a pressure within the range of 2500 to 5000 lbsfper square inch.A

' Pressures in excess of 5000.lbs. per square inch are desirable from the standpointof the degree with its dissolved hydrogen passed out'through tage gained does not balance the increased diiliculties of operation, cost of compression, etc.

When therosin or other chemically active unsaturated compound rst passed .through freshly prepared nickel-aluminum alloy catalyst it will be foundl that the rst samples of'hydrogenated product show a very appreciable nickel content. However, after the `equipment has y -been in operation for aboutu2 to v3 hours the nickel content will be found to dropJ to the order of one part permillion and will remain at this exceedingly low iigure as long as the continuity oi' theprocess ,is maintained. .After an interruption in the process the nickel content'V will 'rise again for a short time and will thenlfall once more to this very low value.

Maximum .beneiits will be derived from the j catalyst employed. This is" due to the cyclic nature of the process, which causes the countercurrent movement of .material'to be hydrogenated and the hydrogenating catalyst. When` the catalyst has become inactive due to long-continued use, its subsequent treatment will depend upon the nature andv valueof the catalyst. For example.lthe catalyst produced by'the surface activation of -pellets of'a nickelaluminum alloy may be reactivated by treatment with `an alkali solution, as for example, a caustic soda solution. Prior Yto thisreactivation treatment, it may be found desirable to extract the spent catalyst with a solvent for the rosin or other compound being hydrogenated. In some cases it will be found advantageous to give the spent catalystl an acid pickle prior to th'e reactivation treatment.

Reactivation of the catalyst may be effected` without interruption in the 'hydrogenation process by merely .cutting out of the battery of reactors, the reactor or reactors whichcontain thespent catalyst and cutting into operation other` tubes which contain reactivated or fresh catalyst. This Voperation ,can even be performed automatically whenever the percentage hydrogenation of the treated product falls below a predetermined value.

While, as indicated above, I prefer touse the concurrent up-fiow systemwhich I have described above, I `may carry out my invention using. a'fconcurrent down-now system in which a mixture of an unsaturated liquid and hydrogen flows downward through the reactors. Such a; system is shown schematically in Figure 3. yIn this Iigure the various' interconnecting conduits and valves necessary to allow the adjustment of the sequence of the reactors have been omitted to reduce the diagram to its` simplest form. The location of such valves and conduits will be analo- -gous to`those used in the.concurrent up-ow system shown in Figure 1 anddescribed in detail.

`It will, of course, be fully appreciated that such A of reactor 63 and so on through the system until vthe Iresulting mixture of hydrogen and hydrogenated rosin emerges from the bottdm of the iinal reator andpasses -through conduit 64 to'a separator 65 from-which hydrogen passes out through conduit 66 and the hydrogenated rosin presents very definite advantages. l i maximum efficiency from the catalyst used, andr conduit 61 to a second separator, not shown, for further separation as `described in connection with the concurrentup-flow system described above.

tem the unsaturated material passes through conduit 68 and enters the reactor 69and 'flows downwai-diy through a catalyst bed containedin. the

reactor, mingling with a stream of hydrogen owingup through Athe catalyst'bed from the l conduit 10. TheA hydrogen leaves the reactor through the conduitl 'Il and passes to the com' pressor/ for re-use. 'Ihe partially hydrogenated material passes out. of the reactor through the conduit 12 to the next reactor and so on throughv the system, inally emerging from thelast reactor through the4 conduit '13 through which it passes to'the separator 'I4 'from which it passes to a second separator not shown, as inthe systems .de-

scribed above. The hydrogen originally enters `yr`the system by passingl into. thelast reactor v' through conduit I5 and fiowsjcounter-current to the .ow of the unsaturated material throughout the`entire system. f

While thev method in accordance with this inven'tioni has been exemplified by, primarily, the

e continuous hydrogenationrofdrosin, it will be appreciated that the method herein described may be used with advantage for continuous hydrogenation'of any unsaturatedorganic materialor other organic material .capable of hydrogenation. .'I'hus, for example, acetone may be reduced to isopropyl alcohol by treatment in' the hydrogenation equipment above described at ordinary temperatures Aand very low hydrogen pressures,v

and cotton seed oil mayy be readily hydrogenated at 160 C. `and 200- lbs. per square inch hydrogen pressure. Other materials such as phenol, naphthalene,.nitrobenzol, furfural, pyridine, castor oil,

"alpha-terpineol, pinene, turpentine Ior dipentene may be readily hydrogenatedeither alone or in solution inl a suitable solvent. Glucose or quinine may/,also be readily hydrogenated when dissolved in a suitable solvent. l' I It will be understood that the -number of reactors which are used in the method and apparatus in accordance with this 'invention can be two or more, as desired.` Lhavefound that I prefer to use a system including ve reactors, 'but a smaller or greater number may be ,used as de'-v sired. e

The method in accordance with this invention It obtains allows the production of a hydrogenated product having a uniform degree of saturation and free v circulating the excess hydrogen at high pressure,

instead vof expanding -it andthen recompressing It will 4be understood that thedetails and ex- 5, 1935 (now United States Patent No. 2,094,117)

amples hereinbefore set forth are illustrative only, and that the invention as herein broadly described and claimed is in no way limited thereby.

This application is a continuation-impart of my application Serial No.` 5067, iiledFebruary granted September 28, 1937. A

-WhatI claim and desire to. protect by Letters Patent is:

1. A method for the continuous hydrogenation of an unsaturated material which contains the hydrocarbon nucleus of a rosin acid, which includes continuously flowing the unsaturated material4 in contact with hydrogen j successively through a plurality-of stationary hydrogenation catalyst beds while under superatmospheric presthrough a. plurality of catalyst beds -in such order sure in excess of about 100 pounds per square inchand at a temperature within the range of about 70 C. to about 300." C., until the activity of the catalystin the beds' has dropped materially, replacing the rst of the catalyst beds 'with a fresh catalyst bed and continuously iiowing the unsaturated material in contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst is the last through which the unsaturated material flows.

2. A method for the continuous hydrogenation of an unsaturated material which contains the hydrocarbon nucleus of a rosin acid, which includes continuously flowing the unsaturated material .in contactjwith hydrogen successively through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about 100 pounds per square inch and at a temperature within the range of about 70 C. to about 300 C., at a rate which varies directly with the activity of the catalyst in the beds, until the 4rate becomes slow, replacing the` iirst of the catalyst beds with a fresh catalyst bed and continuously flowing the unsaturated material in contact with hydrogen throughf a plurality of catalyst beds in such order that the fresh catalyst bed is .the last through which the-unsaturated material flows.

3. A method `for the continuos hydrogenation of an unsaturated material which contains the hydrocarbon nucleus of a rosin acid, which in-` cludes continuously owing the unsaturated material. concurrently with hydrogen successively through a plurality of stationary hydrogenation catalyst bedswhile undersuperatmospheric pressure in excess of about 100 pounds per square.

inch and at a temperature within -the -range of about 70 C. to about 300v Cpat a rate which varies directly with the activity of thel catalyst in ie beds, until the rate becomes slow, replac'- ing the lrst of the catalyst beds with a fresh Vcatalyst bed and continuously flowing thev unsaturated material 'co'ncurrently with hydrogenl that the fresh catalyst bed is the last throug which the unsaturated material iiows.

4. A method for the continuous hydrogenation of an unsaturated material which contains A the hydrocarbon nucleus of a rosin acid, whichA includes continuously flowing the unsaturated material concurrently with hydrogen successively through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pres- -sure in excess of about 100 pounds per square inch and at a temperature within the range of about 10 c. to about 300 c., until the activity of .the catalyst in the beds has dropped materially, replacing the first of the catalyst beds with a fresh catalyst bed and continuously flowing the unsaturated material concurrently with hydrogen -through the plurality of catalyst beds in such dropped materially,l replacing` the rst of the cat-,

alyst beds with a fresh catalyst bed and continu-l ously flowing the unsaturated material 'concurvrently/with hydrogen-upwardly through each of the pluralityvof catalyst-beds in such order that the fresh catalyst bed is the last through which the unsaturated material flows.

6. A method for the ,continuous hydrogenation of a resin which includes continuously iowing a rpsin in liquid phase in contact with hydrogen' successively through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about 100 pounds per square inch and at a temperature within the range of about 70 C.I to about 300 C., until'the activity of the catalyst in the beds has dropped materially, replacing the rst of thecatalyst beds withqa fresh catalyst bed and continuously flowing the r'osin in contact with hydrogen Athrough the plurality of catalyst beds inisuch order that the fresh catalyst bed is the last through which the rosin flows.

7. A method-for the continuous hydrogenation of a rosin which includes continuously flowing a rosin in liquid phase in `contact'with' hydrogen successively through a plurality of stationary hydrogenation catalyst beds while under super- "atmospheric pressure in excess oi about 100 pounds per square inch and at a temperature Within the range of about 70 C. to about 300 C.. at a rate which varies directly with the activity of the catalyst in the beds,.until the rate becomes slow, replacing the rst of the catalyst beds with a fresh catalyst bed and continuously flowing the' rosinin contact with hydrogen through a pluL rality of catalyst beds in such order that the fresh catalyst bed is the last through which the rosin ows. r

8. A method for the continuous hydrogenation of an `unsaturated material which contains the hydrocarbon nucleus of a rosin-acid, which includes -continuously flowing the unsaturated 'ma- -terial while in solution l in an inert solvent in con' Atact with hydrogen successively through a plu-V rality of stationary hydrogenation catalyst bedsl while under superatmospheric lpressure in excess of aboutl 100 pounds per square inch and at a temperature 7Within the range of about 70 C. to

`about 300 c., until the activity .of the catalyst in the beds-has dropped materially, replacing the rst of the catalyst beds with a fresh catalyst bed and continuously flowing the unsaturated material in contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst bed is the last through which the.

unsaturated material ows.

9. A method for the continuous 'hydrogenation of an unsaturated material which contains the hydrocarbon nucleus of a rosin acid; which inlin the beds has dropped materially, replacing the first of the catalyst beds with a fresh catalyst bed and continuously flowing the unsaturated material in'contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst bed is the last through which the unsaturated material flows.

10. A method for the continuous hydrogenation of a rosin in liquid phase in contact with hydrogen successively through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about pounds per square inch and at a temperature within the range of about C. to about 300 C., until the activity of the catalyst inthe beds has dropped materially, replacing the first of the catalyst beds with a fresh catalyst bed and cntinuously flowing the rosin in contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst 'bed is the last through which vthe rosin flows.

11. A method for` the continuous hydrogenation of a rosin in liquid phase in contact with hydrogen successively, through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about 2500 pounds per square inch and at a temperature within the range of about C. to about 220 C., until the yactivity of the catalyst in the beds has dropped materially, replacing the ilrst of the catalyst beds with a fresh catalyst bed and continuously flowing the 4rosin in contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst bed is the last through which the rosin ilows.

12. A method for the continuous hydrogenation of a rosin ester which includes continuously about 3002 C.. until the activity of the catalystl in the bedsehas dropped materially, replacing the first of the catalyst beds with a fresh catalyst contact with hydrogen successively through a to about 300 C., until'the actlvtiy of the catalyst .ously flowing' ab'ietyl alcohol in liquid phase in bed and continuously flowing the rosin ester in contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst bed is the last .through which the rosin ter ilows.

13. A method for the continuous hydrogenation of a rosin alcohol which includes continuously flowing the rosin alcohol in liquid phase in contact with hydrogen successively through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about 100 pounds per square inch and at a temperature within the range of about 70 C. to about 300 C., until the activity ofthe catalyst in the beds has dropped materially, replacing the first of the catalyst beds with a fresh catalyst bedA and continuously flowing the rosin alcohol in contact with hydrogen through the plurality of l catalyst beds in such order that the fresh catalyst bed is the last through which the rosin alcohol flows.

14. A method for the continuous hydrogenation of methyl abietate which includes continuously flowing methyl abietate in liquid phase in plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about 100 pounds per square inch and at a temperature within the range of about 70 C.

in the beds has dropped materially, replacing the first of the catalyst beds with a fresh catalyst bed and continuously .ilowing the methyl abietate in contact with hydrogen through the plurality of catalyst beds in such order that the fresh catalyst bed is the last through which the methyl abietate flows.

l5. A method for the continuous hydrogenation of abietyl alcohol which includes continucontact with hydrogen successively through a plurality of stationary hydrogenation catalyst beds while under superatmospheric pressure in excess of about 100 pounds per square inch and at a temperature within the range 0f about 45 '10 C. to about 300 C., until the activity of the catalyst in the beds'has dropped materially, replacing the rst of the catalyst beds with a fresh catalyst bed and continuously owing the abietyl alcohol in contact with hydrogen through the 5o plurality of catalyst beds ln such order um their' fresh catalyst-bed muelas: throushwmchmi abietyl alcohol ilows.

ROLLIN J. BYRKIT, JR.

han; 

